- Synergistically enhanced performance of transition-metal doped Ni2P for supercapacitance and overall water splitting
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Cost-effective and readily available catalysts applicable for electrochemical conversion technologies are highly desired. Herein, we report the synthesis of dithiophosphonate complexes of the type [Ni{S2P(OH)(4-CH3OC6H4)}2] (1), [Co{S2P(OC4H9)(4-CH3OC6H4)}3] (2) and [Fe{S2P(OH)(4-CH3OC6H4)}3] (3) and employed them to prepare Ni2P, Co-Ni2P and Fe-Ni2P nanoparticles. Ni2P was formed by a facile hot injection method by decomposing complex1in tri-octylphosphine oxide/tri-n-octylphosphine at 300 °C. The prepared Ni2P was doped with Co and Fe employing complexes2and3, respectively, under similar experimental conditions. Doping Ni2P with Co and Fe demonstrated synergistic improvement of Ni2P performance as an electrocatalyst in supercapcitance, hydrogen evololution and oxygen evolution reactions in alkaline medium. Cobalt doping improved the Ni2P charge storage capacity with a supercapacitance of 864 F g?1at 1 A g?1current density. Fe doped Ni2P recorded the lowest overpotential of 259 mV to achieve a current density of 10 mA cm?2and a Tafel slope of 80 mV dec?1for OER, better than the undoped Ni2P and the benchmark IrO2. Likewise, Fe-doped Ni2P electrode required the lowest overpotential of 68 mV with a Tafel slope of 110 mV dec?1to attain the same current density for HER. All catalysts showed excellent stability in supercapacitance and overall water splitting reactions, indicating their practical use in energy conversion technologies.
- Ayom, Gwaza Eric,Choi, Jonghyun,Gupta, Ram Krishna,Khan, Malik Dilshad,Revaprasadu, Neerish,van Zyl, Werner E.
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p. 11821 - 11833
(2021/09/06)
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- Flexible Molecular Precursors for Selective Decomposition to Nickel Sulfide or Nickel Phosphide for Water Splitting and Supercapacitance
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Herein, the synthesis of three nickel(II) dithiophosphonate complexes of the type [Ni{S2P(OR)(4-C6H4OMe)}2] [R=H (1), C3H7 (2)] and [Ni{S2P(OR)(4-C6H4OEt}2] [R=(C6H5)2CH (3)] is described; their structures were confirmed by single-crystal X-ray studies. These complexes were subjected to surfactant/solvent reactions at 300 °C for one hour as flexible molecular precursors to prepare either nickel sulfide or nickel phosphide particles. The decomposition of complex 2 in tri-octylphosphine oxide/1-octadecene (TOPO/ODE), TOPO/tri-n-octylphosphine (TOP), hexadecylamine (HDA)/TOP, and HDA/ODE yielded hexagonal NiS, Ni2P, Ni5P4, and rhombohedral NiS, respectively. Similarly, the decomposition of complex 1 in TOPO/TOP and HDA/TOP yielded hexagonal Ni2P and Ni5P4, respectively, and that of complex 3 in similar solvents led to hexagonal Ni5P4, with TOP as the likely phosphorus provider. Hexagonal NiS was prepared from the solvent-less decomposition of complexes 1 and 2 at 400 °C. NiS (rhom) had the best specific supercapacitance of 2304 F g?1 at a scan rate of 2 mV s?1 followed by 1672 F g?1 of Ni2P (hex). Similarly, NiS (rhom) and Ni2P (hex) showed the highest power and energy densities of 7.4 kW kg?1 and 54.16 W kg?1 as well as 6.3 kW kg?1 and 44.7 W kg?1, respectively. Ni5P4 (hex) had the lowest recorded overpotential of 350 mV at a current density of 50 mA cm?2 among the samples tested for the oxygen evolution reaction (OER). NiS (hex) and Ni5P4 (hex) had the lowest overpotentials of 231 and 235 mV to achieve a current density of 50 mA cm?2, respectively, in hydrogen evolution reaction (HER) examinations.
- Ayom, Gwaza E.,Gupta, Ram K.,Ingsel, Tenzin,Khan, Malik D.,Lin, Wang,Revaprasadu, Neerish,Zamisa, Sizwe J.,van Zyl, Werner E.
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p. 2693 - 2704
(2020/03/04)
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- Sulfur-rich nickel(II) complex: Synthesis, characterization, and X-ray crystal structure
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A sulfur-rich nickel complex has been synthesized by the reaction between 2,4-bis(4-methoxyphenyl)- 1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson’s reagent) and Ni(NO3)2·6H2O in 2-propanol. The complex has been characterized by elemental analysis, IR,1H NMR,13C NMR, and31P NMR spectroscopies and molar conductivity. Also, the crystal structure of the complex has been investigated by X-ray diffraction, which illustrates a slightly distorted square planar environment around Ni(II) ion in solid. Furthermore, the crystal structure of the complex shows 3D network through intermolecular C-H…Ni, CH O, and C-H S hydrogen bonds and C–H π interaction.
- Jafari, Hadi,Zarei, Seyed Amir
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p. 260 - 263
(2017/08/10)
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- Syntheses, characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates
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Some 1,3-dithiadiphosphetane 2,4-disulfides (X2P2S4, X: Fc, FcLR; X: CH3O?C6H4?, LR) were allowed to react with alcohols to obtain dithiophosphonic acids (X(OR)PS2H). These were converted to the corresponding ammonium salts. The salts were of the structures [Fc(OR)PS2]?[NH4]+, R: 3-methyl-1-butyl- for I; 1-phenyl-1-propyl- for II; 3-pentyl- for III; 3-phenyl-1-propyl- for IV and [CH3O?C6H4(OR)PS2]?[NH4]+, R: 3-methyl-1-butyl- for V and 1-phenyl-1-propyl- for VI. To the best of our knowledge, all the compounds except V were prepared for the first time. The compounds synthesized were characterized by elemental analysis, NMR (1H,13C,31P), MS, FTIR, and Raman spectroscopies. Electrochemical behaviors of I–VI at disposable pencil graphite electrode (PGE) were investigated by using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Adsorption and diffusion patterns of all the compounds on the PGE were also studied. Two electroactive groups were identified in the compounds I–IV and only one in V and VI. The ferrocenyl groups of I-IV were oxidized at around 0.4?V. The same compounds display a second, more intense CV band at 0.8?V. The corresponding band for the compounds V–VI appears at around 0.6?V with a much weaker intensity. It is suggested that the ferrocenyl group introduced into the structures stabilizes the radical species formed as the product of the oxidation of the dithiophosphonato group.
- Sa?lam, Ertu?rul Gazi,Erden, Sevcan,Tutsak, ?zgür,Bayraktepe, Dilek Eskik?y,Durmu?, Zehra Yazan,Dal, Hakan,Ebin?, Ahmet
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p. 322 - 329
(2017/02/18)
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- Preparation method and application of multifunctional ultraviolet absorbent
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The invention relates to a preparation method and application of a multifunctional ultraviolet absorbent for terylene. The general structural formula of the absorbent is as follows: formula, wherein Y is a quaternary ammonium salt group. According to the preparation method and application of the multifunctional ultraviolet absorbent for terylene disclosed by the invention, the dyeing mode of the ultraviolet absorbent to terylene is similar to disperse dyes, and fabrics can be subjected to anti-ultraviolet finishing by using a high-temperature and high-pressure exhausting method and can also be dyed with the disperse dyes in the same bath; the finished fabrics not only have good anti-ultraviolet properties, but also have the effects of killing or inhibiting Gram-positive bacteria and Gram-negative bacteria represented by staphylococcus aureus and Escherichia coli; and meanwhile, the fabrics have good anti-static function.
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Paragraph 0048; 0049; 0050
(2017/04/28)
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- An Aluminum(III)-Catalyzed Thioamide-Aldehyde-Styrene Condensation: Direct Synthesis of Allylic Thioamide Derivatives
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An aluminum(III) triflate catalyzed three-component synthesis of allylic thioamide derivatives by condensation of a thioamide, paraformaldehyde and a styrene is reported.
- Xu, Bin,Zhong, Xue,Wang, Xi-Cun,Quan, Zheng-Jun
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supporting information
p. 2237 - 2240
(2016/11/07)
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- A highly selective and naked-eye sensor for Hg2+ based on quinazoline-4(3H)-thione
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A highly selective colorimetric and fluorescent sensor for Hg2+, TPS (TPS = 2-(4-(diphenyl-amino)phenyl)quinazoline-4(3H)-thione), based on a 2-substituted quinazoline-4(3H)-thione derivative, was designed and characterized in this paper. TPS displays relatively strong fluorescence centered at about 468 nm. When mixing with Hg2+, TPS interacts with Hg2+ in a 2:1(TPS-Hg2+) stoichiometry via a coordination bond interaction between the sulfur atom and Hg2+ with an association constant of 4.17 × 108 M-2 (R2 = 0.96). Upon addition of Hg2+, TPS showed a remarkable decrease in fluorescence spectra (468 nm) with a clear color change from yellow to red, so TPS could serve as a naked-eye sensor for Hg2+. The sensor allow determination of Hg2+ in the working range 2.0 μM-12.0 μM with a detection limit of 1.5 μM. Upon addition of KI to the solution of TPS-Hg2+ species, the spectra can be restored to the original spectrum in both absorption and fluorescence and indicates that this sensor could be reused. The sensor exhibited excellent reproducibility, reversibility and selectivity.
- Mei, Qunbo,Wang, Lingxia,Tian, Bo,Yan, Fang,Zhang, Bin,Huang, Wei,Tong, Bihai
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experimental part
p. 1879 - 1883
(2012/10/08)
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- 1,4-OXAZEPINES AS BACE1 AND/OR BACE2 INHIBITORS
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The present invention relates to 1,4 Oxazepines of formula I having BACE1 and/or BACE2 inhibitory activity, their manufacture, pharmaceutical compositions containing them and their use as therapeutically active substances. The active compounds of the present invention are useful in the therapeutic and/or prophylactic treatment of e.g. Alzheimer's disease and type 2 diabetes.
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Page/Page column 48
(2012/10/08)
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- Derivatives of 4- or 5-aminosalicylic acid
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The present invention provides new derivatives of 4- or 5-aminosalicylic acid, and a pharmaceutical composition containing these derivatives of 4- or 5-aminosalicylic acid as active ingredients, useful for the treatment of intestinal diseases such as inflammatory bowel disease (IBD) and irritable bowel syndrome (IBS) and for the prevention/treatment of colon cancer. More particularly, these derivatives comprise a hydrogen sulfide releasing moiety linked via an azo, an ester, an anhydride, a thioester or an amide linkage to a molecule of 4- or 5-aminosalicylic acid. Furthermore, the present invention provides a process for preparing these compounds and their use for treating IBD and IBS and the prevention/treatment of colon cancer.
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Page/Page column 18-19; 24
(2008/06/13)
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- Thiophosphonate inhibitors of phosphatase enzymes and metallophosphatases
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Compounds of the general formula wherein R is selected from the group consisting essentially of hydrogen, methyl, ethyl, phenyl, a carboxyl, or naphthyl substituted or a carbonyl substituted, alkyl of from 3 to 20 carbon atoms, a mono, bi or tri cyclic aryl or substituted aryl for the inhibition of phosphatase enzymes, including metallophosphatases; and, novel methods for synthesizing such compounds. The methods of use include the administration of an effective amount of the compound to provide effective phosphatase inhibition and therapeutic use to treat or prevent certain diseases, which utilize specific phosphatase enzymes.
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Page/Page column 11
(2010/02/11)
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- Thiophosphonate inhibitors of phosphatase enzymes and metallophosphatases
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Compounds of the general formula wherein R is selected from the group consisting essentially of hydrogen, methyl, ethyl, phenyl, a carboxyl, or naphthyl substituted or a carbonyl substituted, alkyl of from 3 to 20 carbon atoms, a mono, bi or tri cyclic aryl or substituted aryl for the inhibition of phosphatase enzymes, including metallophosphatases; and, novel methods for synthesizing such compounds. The methods of use include the administration of an effective amount of the compound to provide effective phosphatase inhibition and therapeutic use to treat or prevent certain diseases, which utilize specific phosphatase enzymes.
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- A general and convenient route to dithiophosphonate salt derivatives
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2,4-Diaryl and 2,4-diferrocenyl-1,3-dithiadiphosphetane disulfide dimers, (RP(S)S)2, where R = Ph (1a), 4-C6H4OMe (1b) or ferrocenyl (Fc) (1c) react with a variety of alcohols, silanols, or trialkylsilylalcohols to form dithiophosphonic acids in a one-flask procedure. The generated acids have a relatively strong acidity which, upon deprotonation, facilitates the facile high yield conversion to monoanionic salts of the type [S2PR(OR′)]. The present study reports the systematic preparation of these salts with variation in both R and especially R′ groups. Compounds were characterized by 31P{1H} NMR spectroscopy and elemental analysis. High quality single crystals of (1a) were obtained from the slow cooling of a viscous melt which allowed for the X-ray crystal structure to be determined. Qualitative solubility data have been obtained for several of the isolated salts to provide valuable information for synthesis design, especially with regard to metal complexation. The title salts are effective precursors to obtain a series of new transition-metal complexes both in aqueous and non-aqueous solvents.
- Van Zyl, Werner E.,Fackler, John P.
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p. 117 - 132
(2007/10/03)
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- Phenylimidazolidines having antiandrogenic activity
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A compound of the formula STR1 wherein R1 is --CN, --NO2 or halogen, R2 is --CF3 or halogen, --A--B-- is of STR2 X is --O-- or --S--, R3 is hydrogen, alkyl, alkenyl or alkynyl of up to 12 carbon atoms, aryl and aralkyl of up to 12 carbon atoms, all optionally substituted by --OH, halogen, --SH, --CN, acyl and acyloxy of up to 7 carbon atoms, --aryl, --O--aryl, --O--aralkyl --S-- aryl of up to 12 carbon atoms the aryl and aralkyl being optionally substituted by halogen, --CF3, alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl or alkynyloxy with the sulfur being optionally oxidized to sulfone or sulfoxide, free, esterified, amidified or salified carboxy, --NH2, mono and dialkylamino and heterocyclic of 3 to 6 ring members and containing at least one heteroatom selected from the group consisting of oxygen, sulfur and nitrogen, the alkyl, alkenyl and alkynyl being optionally interrupted by at least one oxygen, nitrogen or sulfur optionally oxidized to sulfoxide or sulfone, trialkylsilyl with the alkyl having 1 to 6 carbon atoms and acyl and acyloxy of an organic carboxylic acid of 1 to 7 carbon atoms and Y is --O--, --S-- or --NH--, except the compounds wherein --A-B-- is STR3 X is oxygen, R3 is hydrogen and Y is oxygen or --NH--, R2 is --CF3 or halogen and R1 is --NO2 or halogen and their non-toxic, pharmaceutically acceptable acid addition salts.
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- Phenylimidazolidines having antiandrogenic activity
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A compound of the formula STR1 wherein R 1 is --CN, --NO 2 or halogen, R 2 is --CF 3 or halogen, --A-B-- is of STR2 X is --O-- or --S--, R 3 is hydrogen, alkyl, alkenyl or alkynyl of up to 12 carbon atoms, aryl and aralkyl of up to 12 carbon atoms, all optionally substituted by --OH, halogen, --SH, --CN, acyl and acyloxy of up to 7 carbon atoms, --aryl, --O--aryl, --O--aralkyl --S-- aryl of up to 12 carbon atoms the aryl and aralkyl being optionally substituted by halogen, --CF 3, alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl or alkynyloxy with the sulfur being optionally oxidized to sulfone or sulfoxide, free, esterified, amidified or salified carboxy, --NH 2, mono and dialkylamino and heterocyclic of 3 to 6 ring members and containing at least one heteroatom selected from the group consisting of oxygen, sulfur and nitrogen, the alkyl, alkenyl and alkynyl being optionally interrupted by at least one oxygen, nitrogen or sulfur optionally oxidized to sulfoxide or sulfone, trialkylsilyl with the alkyl having 1 to 6 carbon atoms and acyl and acyloxy of an organic carboxylic acid of 1 to 7 carbon atoms and Y is --O--, --S-- or --NH--, except the compounds wherein --A-B-- is STR3 X is oxygen, R 3 is hydrogen and Y is oxygen or --NH--, R 2 is --CF 3 or halogen and R 1 is --NO 2 or halogen and their non-toxic, pharmaceutically acceptable acid addition salts.
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- Metal complexes, the preparation thereof and use as biocides
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A metal complex of the general formula, [R1CSNRO]xM(L)y, where R and R1 are optionally substituted hydrocarbyl groups, M is a metal of Group IIIA to VA and IB to VIIB, with the exception of copper, L is a ligand, x has a value of 1 to 3 and y is zero or has a value of up to 4. The complex may be prepared by the reaction of a metal salt with an N-hydroxythiobenzamide. Complexes of this type have anti-microbial properties, and can be used as industrial biocides.
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- DIE STRUKTUR VON ALKYL- UND ARYLPERTHIOPHOSPHONSAEUREANHYDRIDEN IN LOESUNG
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The analysis of 1H-, 31P- and 13C-NMR spectra of different alkyl- and arylperthiophosphonic acid anhydrides shows that these compounds prefer a dimeric structure in solution.They exist as 2,4-diorganyl-2,4-dithioxo-1,3,2λ5,4λ5-dithiadiphosphetanes.Most of the perthiophosphonic acid anhydrides form configuration isomers which differ in the position of the thioxo groups relatively to the ring plane.The concentration of the trans-isomer is generally larger than that of the cis-isomer.The ratio of the concentration of both isomers is obviously determined by the polarity of the solvent used.Mixing of solutions of different perthiophosphonic acid anhydrides results in unsymmetrical compounds also existing in cis- and trans-configuration. 31P chemical shifts and geminal P-P coupling constants for symmetrical and unsymmetrical perthiophosphonic acid anhydrides are presented and discussed. - Key words: 31P chemical shifts; P-P coupling constants; perthiophosphonic acid anhydrides; mixed perthiophosphonic acid anhydrides; configuration isomers; 2,4-diorganyl-2,4-dithioxo-1,3,2λ5,4λ5-dithiadiphosphetanes.
- Ohms, Gisela,Treichler, Antje,Grossmann, Gisbert
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- GAS-PHASE PYROLYSIS OF TERVALENT PHOSPHORUS-OXY AND -THIA HETEROCYCLES: A NEW APPROACH TO SHORT-LIVED PENTAVALENT PHOSPHORUS COMPOUNDS HAVING CO-ORDINATION NUMBER 3
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Generation of short-lived metaphosphonates by thermal fragmentation of cyclic phosphonites and their thia-analogues in the gas phase is described, including an elaboration of the method whereby a monomeric phosphonobenzene is detected unambiguously for the first time by an intra-molecular trapping reaction which also illustrates the considerable potential of such species in the synthesis of phosphorus heterocycles.
- Cadogan, J. I. G.,Bracher, Simon,Gosney, Ian,Yaslak, Salih
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p. 229 - 232
(2007/10/02)
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